Photopolymerizable composition including a photopolymerization initiation system having excellent light sensitivity to visible light

ABSTRACT

A photopolymerizable composition is described, comprising components (i) a compound having at least one addition-polymerizable ethylenically unsaturated bond, (ii) a compound represented by the following formula (I): ##STR1## and (iii) an activating agent which generates an active radical upon light irradiation in the co-presence of component (ii). The substituents in formula (I) are defined in the specification.

FIELD OF THE INVENTION

The present invention relates to a photopolymerizable composition. Morespecifically, the present invention relates to a photopolymerizablecomposition comprising a novel photopolymerization initiation systemhaving excellent light sensitivity to visible light.

BACKGROUND OF THE INVENTION

The photopolymerizable composition is a material which changes itsphysical properties of the composition as a result of polymerizationreaction induced by light irradiation and is widely used in the fieldsof printing, printed circuit, fine processing such as ultra LSI,painting, ink, hologram recording and three dimensional modeling. Theapplication of the composition is thus more and more expanding. Thephotopolymerizable composition fundamentally comprises anaddition-polymerizable ethylenically unsaturated compound and aphotopolymerization initiator. The composition undertakes polymerizationupon light irradiation and thereby is cured and insolubilized.Consequently, when the photosensitive composition having further addedthereto, if desired, a binder resin having a film-forming ability and athermal polymerization inhibitor is formed into an appropriate film andsubjected to light irradiation through a desired negative image and onlythe non-irradiated area is removed by a proper solvent (hereinafterreferred to simply as "development"), a desired cured image can beformed. Such an image formation method is well known very useful inpreparing a printing plate.

The photopolymerization initiator conventionally used in thephotopolymerizable composition includes benzil, benzoin ether, Michler'sketone, anthraquinone, acridine, phenazine or benzophenone. However, thecomposition comprising such a photopolymerization initiator is low inthe photospeed and more remarkably poor in the photopolymerizationability to visible light at 400 nm or more than the photopolymerizationability to light in the ultraviolet wavelength region of 400 nm or less.Accordingly, the photopolymerizable composition comprising aconventional photopolymerization initiator is strictly limited on theapplication range thereof.

Furthermore, photosensitive composition highly curable upon lightirradiation in a small quantity has been long demanded. The compositionis useful as a photosensitive material suitable, for example, forprojection exposure of non-contact type. Further, in recent years, theimage information technique using a visible laser has come into apractical use stage and accordingly, a photosensitive composition havinga high photopolymerization ability to visible light has been keenlydemanded. The visible laser light which is very expected for use in sucha method is an Ar⁺ laser light having a wavelength of 488 nm or aYAG-SHG laser light having a wavelength of 532 nm.

With respect to the photopolymerizable composition comprising aphotopolymerization initiation system sensitive to visible light,several proposals have been hitherto made. For example, U.S. Pat. No.2,850,445 has reported that a certain kind of photosensitive dyes, suchas Rose Bengal, eosine, and erythrosine, exhibit effective sensitivityto visible light. Also, improved techniques hitherto proposed include acomposite initiation system containing a dye and an amine (JP-B-44-20189(the term "JP-B" as used herein means an "examined Japanese patentpublication")), a system containing a hexaarylbiimidazole, a radicalgenerating agent and a dye (JP-B-45-37377), a system containinghexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-2528,JP-A-54-155292 (the term "JP-A" as used herein means an "unexaminedpublished Japanese patent application")), a system containing a3-ketocoumarin compound and an active halogen compound (JP-A-58-15503)and a system containing a substituted triazine and a merocyanine dye(JP-A-54-15102). These techniques are surely effective to visible lightbut, in practical viewpoint, the sensitivity is practicallyinsufficient. JP-A-2-244050 proposes a system containing a dye having a4-thiazolidinone skeleton and a radical generating agent as a highlysensitive initiation system. This system is surely highly sensitive;however, the sensitivity is still insufficient and an initiation systemon a higher level has been demanded. Further, with respect to theabove-described dye, its low compatibility with other componentsconstituting the composition is a serious bar to practical use thereof.In other words, as a result, in adding the dye to a photosensitivematerial, its concentration is limited to be low, and the dyeprecipitates during the storage to cause undesirable change inproperties, such as deterioration of the photosensitivity.

Moreover, a system using a sensitizer having various 1-indanoneskeletons is proposed in JP-B-59-28329, JP-A-5-210240, JP-A-5-216226,JP-A-6-35198 and JP-A-6-295061; however, the system is not satisfactoryin practice and improvement is demanded.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a high-sensitivephotopolymerizable composition, more specifically, a photopolymerizablecomposition comprising a photopolymerization initiator capable ofincreasing the photopolymerization rate of a photopolymerizationcomposition containing an addition-polymerizable, ethylenicallyunsaturated compound.

Another object of the present invention is to provide aphotopolymerizable composition containing a photopolymerizationinitiator having high sensitivity to visible light at 400 nm or more,particularly even to light at around 488 nm and 532 nm corresponding tothe outputs of an Ar⁺ laser and a YAG-SHG laser, respectively.

Still another object of the present invention is to provide aphotopolymerizable composition for use as a photosensitive materialhaving excellent storage stability.

As a result of intensive investigations to achieve the above-describedobjects, the present inventors have found that a photopolymerizablecomposition containing a specific photopolymerization initiation systemexhibits an extremely high photopolymerization rate, also exhibits highphotosensitivity even to visible light rays of 400 nm or more, and isexcellent in the storage stability, and they have accomplished thepresent invention.

More specifically, these and other objects of the present invention havebeen attained by a photopolymerizable composition comprising thefollowing components (i), (ii) and (iii):

(i) a compound having at least one addition-polymerizable ethylenicallyunsaturated bond;

(ii) a compound represented by the following formula (I): ##STR2##wherein R represents a halogen atom, an alkyl group, a substituted alkylgroup, an aryl group, a substituted aryl group or a substituted carbonylgroup; R¹ and R² each independently represents an alkyl group, asubstituted alkyl group, an aryl group or a substituted aryl group; R³,R⁴, R⁵ and R⁶ each independently represents a hydrogen atom, a hydroxylgroup, an alkyl group, a substituted alkyl group, a substituted oxygroup or a substituted thio group; or R¹ and R³, or R² and R⁵ may becombined with each other to form a ring structure; R⁷, R⁸, R⁹ and R¹⁰each independently represents a hydrogen atom, a halogen atom, an alkylgroup, a substituted alkyl group, an aryl group, a substituted arylgroup, a hydroxyl group, a substituted oxy group, a mercapto group, asubstituted thio group, an amino group, a substituted amino group, asubstituted carbonyl group, a substituted sulfonyl group, a cyano groupor a nitro group; or R⁷ and R⁸, R⁸ and R⁹, or R⁹ and R¹⁰ may be combinedwith each other to form an aliphatic or aromatic ring; and m represents0 or 1; and

(iii) an activating agent which generates an active radical upon lightirradiation in the co-presence of component (ii).

DETAILED DESCRIPTION OF THE INVENTION

Each component of the photopolymerizable composition of the presentinvention will be described below in detail.

The compound having at least one addition-polymerizable ethylenicallyunsaturated bond as component (i) used in the present invention isselected from the compounds having at least one, preferably two or more,ethylenically unsaturated terminal bonds.

The compound has a chemical form such as a monomer, a polymer, morespecifically, a dimer, a trimer or an oligomer, a mixture of these or acopolymer of these. Examples of the monomer and copolymer thereofinclude esters of an unsaturated carboxylic acid (e.g., acrylic acid,methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleicacid) with an aliphatic polyhydric alcohol compound, and amides of anunsaturated carboxylic acid with an aliphatic polyhydric amine compound.

Specific examples of the monomer for the ester of an aliphaticpolyhydric alcohol compound with an unsaturated carboxylic acid include:

acrylic ester, such as ethylene glycol diacrylate, triethylene glycoldiacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate,propylene glycol diacrylate, neopentyl glycol diacrylate,trimethylolpropane triacrylate, trimethylolpropanetri(acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanedioldiacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycoldiacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate,pentaerythritol tetraacrylate, dipentaerythritol diacrylate,dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitoltetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,tri(acryloyloxyethyl)isocyanurate, and polyester acrylate oligomer;

methacrylic ester, such as tetramethylene glycol dimethacrylate,triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate,trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate,ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate,hexanediol dimethacrylate, pentaerythritoldimethacrylate,pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate,dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate,sorbitol trimethacrylate, sorbitol tetramethacrylate, bisp-(3-methacryloxy-2-hydroxypropoxy)-phenyl!dimethylmethane, and bisp-(methacryloxyethoxy)phenyl!-dimethylmethane;

itaconic ester, such as ethylene glycol diitaconate, propylene glycoldiitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate,tetramethylene glycol diitaconate, pentaerythritol diitaconate, andsorbitol tetraitaconate;

crotonic ester, such as ethylene glycol dicrotonate, tetramethyleneglycol dicrotonate, pentaerythritol dicrotonate, and sorbitoltetradicrotonate;

isocrotonic ester, such as ethylene glycol diisocrotonate,pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate;

maleic ester, such as ethylene glycol dimaleate, triethylene glycoldimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate; and

a mixture of the above-described ester monomers.

Examples of the monomer for the amide of an aliphatic polyhydric aminecompound with unsaturated carboxylic acid includemethylenebisacrylamide, methylenebismethacrylamide,1,6-hexamethylenebisacrylamide, 1,6-hexamethylene-bismethacrylamide,diethylenetriaminetrisacrylamide, xylylenebisacrylamide, andxylylenebismethacrylamide.

Other examples include a vinyl urethane compound having two or morepolymerizable vinyl groups in one molecule resulting from the additionof a vinyl monomer having a hydroxyl group represented by the followingformula (D) to a polyisocyanate compound having two or more isocyanategroups in one molecule described in JP-B-48-41708:

    CH.sub.2 ═C(R')COOCH.sub.2 CH(R")OH                    (D)

wherein R' and R" each represents H or CH₃.

Also, a polyfunctional acrylate or methacrylate such as urethaneacrylates described in JP-A-51-37193, polyester acrylates described inJP-A-48-64183, JP-B-49-43191 and JP-B-52-30490 and epoxy acrylatesresulting from the reaction of an epoxy resin with a (meth)acrylic acidare included. Further, those described as a photocurable monomer oroligomer in Nippon Secchaku Kyokaishi, Vol. 1, 20, No. 7, pp. 300-308(1984) may be used. The above-described monomer or prepolymer is used inan amount of from 5 to 70% by weight (hereinafter referred to simply as"%"), preferably from 10 to 50%, based on the entire components.

The component (ii) for use in the present invention is a compoundrepresented by formula (I) above.

Examples of R in formula (I) are shown below.

The halogen atom includes --F, --Br, --Cl and --I. Among these, --Cl and--Br are more preferred.

The alkyl group includes linear, branched and cyclic alkyl groups eachhaving from 1 to 20 carbon atoms. Specific examples thereof include amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, adecyl group, a undecyl group, a dodecyl group, a tridecyl group, ahexadecyl group, an octadecyl group, an eicosyl group, an isopropylgroup, an isobutyl group, an s-butyl group, a t-butyl group, anisopentyl group, a neopentyl group, a 1-methylbutyl group, an isohexylgroup, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group,a cyclopentyl group and 2-norbornyl group. Among these, a linear alkylgroup having from 1 to 12 carbon atoms, a branched alkyl group havingfrom 3 to 12 carbon atoms and a cyclic alkyl group having from 5 to 10carbon atoms are more preferred.

The substituent for the substituted alkyl group includes a monovalentnonmetallic atom group excluding hydrogen and preferred examples thereofinclude a halogen atom (e.g., --F, --Br, --Cl, --I), a hydroxyl group,an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group,an arylthio group, an alkyldithio group, an aryldithio group, an aminogroup, an N-alkylamino group, an N,N-dialkylamino group, an N-arylaminogroup, an N,N-diarylamino group, an N-alkyl-N-arylamino group, anacyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, anN-arylcarbamoyloxy group, an N,N-dialkylcarbamoyloxy group, anN,N-diarylcarbamoyloxy group, an N-alkyl-N-arylcarbamoyloxy group, analkylsulfoxy group, an arylsulfoxy group, an acylthio group, anacylamino group, an N-alkylacylamino group, an N-arylacylamino group, aureido group, an N'-alkylureido group, an N',N'-dialkylureido group, anN'-arylureido group, an N',N'-diarylureido group, anN'-alkyl-N'-arylureido group, an N-alkylureido group, an N-arylureidogroup, an N'-alkyl-N-alkylureido N'-alkyl-N-alkylureido group, anN',N'-dialkyl-N-alkylureido group, an N,N,-dialkyl-N-arylureido group,an N'-aryl-N-alkylureido group, an N'-aryl-N-arylureido group, anN',N'-diaryl-N-alkylureido group, an N',N'-diaryl-N-arylureido group, anN'-alkyl-N'-aryl-N-alkylureido group, an N'-alkyl-N'-aryl-N-arylureidogroup, an alkoxycarbonylamino group, an aryloxycarbonylamino group, anN-alkylalkoxycarbonylamino group, an N-alkylaryloxycarbonylamino group,an N-arylalkoxycarbonylamino group, an N-arylaryloxycarbonylamino group,a formyl group, an acyl group, a carboxyl group, an alkoxycarbonylgroup, an aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoylgroup, an N,N-dialkylcarbamoyl group, an N-arylcarbamoyl group, anN,N-diarylcarbamoyl group, an N-alkyl-N-arylcarbamoyl group, analkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, anarylsulfonyl group, a sulfo group (--SO₃ H) and a conjugate base groupthereof (hereinafter referred to as a sulfonate group), analkoxysulfonyl group, an aryloxysulfonyl group, a sulfinamoyl group, anN-alkylsulfinamoyl group, an N,N-dialkylsulfinamoyl group, anN-arylsulfinamoyl group, an N,N-diarylsulfinamoyl group, anN-alkyl-N-arylsulfinamoyl group, a sulfamoyl group, an N-alkylsulfamoylgroup, an N,N-dialkylsulfamoyl group, an N-arylsulfamoyl group, anN,N-diarylsulfamoyl group, an N-alkyl-N-arylsulfamoyl group, a phosphonogroup (--PO₃ H₂) and a conjugate base group thereof (hereinafterreferred to as a phosphonate group), a dialkylphosphono group (--PO₃(alkyl)₂), a diarylphosphono group (--PO₃ (aryl)₂), analkylarylphosphono group (--PO₃ (alkyl)(aryl)), a monoalkylphosphonogroup (--PO₃ H(alkyl)) and a conjugate base group thereof (hereinafterreferred to as an alkylphosphonate group), a monoarylphosphono group(--PO₃ H(aryl)) and a conjugate base group thereof (hereinafter referredto as an arylphosphonate group), a phosphonoxy group (--OPO₃ H₂) and aconjugate base group thereof (hereinafter referred to as a phosphonatoxygroup), a dialkylphosphonoxy group (--OPO₃ (alkyl)₂), adiarylphosphonoxy group (--OPO₃ (aryl)₂), an alkylarylphosphonoxy group(--OPO₃ (alkyl)(aryl)), a monoalkylphosphonoxy group (--OPO₃ H(alkyl))and a conjugate base group thereof (hereinafter referred to as analkylphosphonatoxy group), a monoarylphosphonoxy group (--OPO₃ H(aryl))and a conjugate base group thereof (hereinafter referred to as anarylphosphonatoxy group), a cyano group, a nitro group, and an arylgroup. Specific examples of the alkyl group in these substituentsinclude the above-described alkyl groups and specific examples of thearyl group include a phenyl group, a biphenyl group, a naphthyl group, atolyl group, a xylyl group, a mesityl group, a cumenyl group, achlorophenyl group, a bromophenyl group, a chloromethylphenyl group, ahydroxyphenyl group, a methoxyphenyl group, an ethoxyphenyl group, aphenoxyphenyl group, an acetoxyphenyl group, a benzoyloxyphenyl group, amethylthiophenyl group, a phenylthiophenyl group, a methylaminophenylgroup, a. dimethylaminophenyl group, an acetylaminophenyl group, acarboxyphenyl group, a methoxycarbonylphenyl group, anethoxycarbonylphenyl group, a phenoxycarbonylphenyl group, anN-phenylcarbamoylphenyl group, a phenyl group, a cyanophenyl group, asulfophenyl group, a sulfonate phenyl group, a phosphonophenyl group anda phosphonate phenyl group. R¹¹ in the acyl group (R¹¹ CO--) includesthe above-described alkyl, substituted alkyl, aryl and substituted arylgroups. Among these substituents, more preferred are a halogen atom(--F, --Br, --Cl, --I), an alkoxy group, an aryloxy group, an alkylthiogroup, an arylthio group, an N-alkylamino group, an N,N-dialkylaminogroup, an acyloxy group, an N-alkylcarbamoyloxy group, anN-arylcarbamoyloxy group, an acylamino group, a formyl group, an acylgroup, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonylgroup, a carbamoyl group, an N-alkylcarbamoyl group, anN,N-dialkylcarbamoyl group, an N-arylcarbamoyl group, anN-alkyl-N-arylcarbamoyl group, a sulfo group, a sulfonate group, asulfamoyl group, an N-alkylsulfamoyl group, an N,N-dialkylsulfamoylgroup, an N-arylsulfamoyl group, an N-alkyl-N-arylsulfamoyl group, aphosphono group, a phosphonate group, a dialkylphosphono group, adiarylphosphono group, a monoalkylphosphono group, an alkylphosphonategroup, a monoarylphosphono group, an arylphosphonate group, aphosphonooxy group, a phosphonate oxy group, and an aryl group. Thealkylene group in the substituted alkyl group includes a divalentorganic residue resulting from eliminating any one of hydrogen atoms onthe above-described alkyl group having from 1 to 20 carbon atoms andpreferred are a linear alkylene group having from 1 to 12 carbon atoms,a branched alkylene group having from 3 to 12 carbon atoms and a cyclicalkylene group having from 5 to 10 carbon atoms. Preferred examples ofthe substituted alkyl group include a chloromethyl group, a bromomethylgroup, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethylgroup, a methoxyethoxyethyl group, an allyloxymethyl group, aphenoxymethyl group, a methylthiomethyl group, a tolylthiomethyl group,an ethylaminoethyl group, a diethylaminopropyl group, a morpholinopropylgroup, an acetyloxymethyl group, a benzoyloxymethyl group, anN-cyclohexylcarbamoyloxyethyl group, an N-phenylcarbamoyloxyethyl group,an acetylaminoethyl group, an N-methylbenzoylaminopropyl group, a2-oxoethyl group, a 2-oxopropyl group, a carboxypropyl group, amethoxycarbonylethyl group, an allyloxycarbonylbutyl group, achlorophenoxycarbonylmethyl group, a carbamoylmethyl group, anN-methylcarbamoylethyl group, an N,N-dipropylcarbamoylmethyl group, anN-(methoxyphenyl)carbamoylethyl group, an N-methyl-N-(sulfophenyl)carbamoylmethyl group, a sulfobutyl group, a sulfonatobutyl group, asulfamoylbutyl group, an N-ethylsulfamoylmethyl group, anN,N-dipropylsulfamoylpropyl group, an N-tolylsulfamoylpropyl group, anN-methyl-N-(phosphonophenyl) sulfamoyloctyl group, a phosphonobutylgroup, a phosphonatohexyl group, a diethylphosphonobutyl group, adiphenylphosphonopropyl group, a methylphosphonobutyl group, amethylphosphonatobutyl group, a tolylphosphonohexyl group, atolylphosphonatohexyl group, a phosphonoxypropyl group, aphosphonatoxybutyl group, a benzyl group, a phenethyl group, anα-methylbenzyl group, a 1-methyl-1-phenylethyl group, a p-methylbenzylgroup, a cinnamyl group, an allyl group, a 1-propenylmethyl group, a2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group,a 2-propynyl group, a 2-butynyl group and a 3-butynyl group.

The aryl group includes a condensed ring formed by from 1 to 3 benzenerings or a condensed ring formed by a benzene ring and a 5-memberedunsaturated ring, and specific examples thereof include a phenyl group,a naphthyl group, an anthryl group, a phenanthryl group, an indenylgroup, an acenaphthenyl group and a fluorenyl group, with the phenylgroup and the naphthyl group being preferred.

The substituted aryl group includes those having a monovalentnonmetallic atom group exclusive of hydrogen as a substituent on thering-forming carbon atoms of the above-described aryl group. Preferredexamples of the substituent include the above-described alkyl groups,substituted alkyl groups and substituents for the substituted alkylgroup. Preferred specific examples of the substituted aryl group includea biphenyl group, a tolyl group, a xylyl group, a mesityl group, acumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenylgroup, a chloromethylphenyl group, a trifluoromethylphenyl group, ahydroxyphenyl group, a methoxyphenyl group, a methoxyethoxyphenyl group,an allyloxyphenyl group, a phenoxyphenyl group, a methylthiophenylgroup, a tolylthiophenyl group, an ethylaminophenyl group, adiethylaminophenyl group, a morpholinophenyl group, an acetyloxyphenylgroup, a benzoyloxyphenyl group, an N-cyclohexylcarbamoyloxyphenylgroup, an N-phenylcarbamoyloxyphenyl group, an acetylaminophenyl group,an N-methylbenzoylaminophenyl group, a carboxyphenyl group, amethoxycarbonylphenyl group, an allyloxycarbonylphenyl group, achlorophenoxycarbonylphenyl group, a carbamoylphenyl group, anN-methylcarbamoylphenyl group, an N, N-dipropylcarbamoylphenyl group, anN-(methoxyphenyl)-carbamoylphenyl group, anN-methyl-N-(sulfophenyl)-carbamoylphenyl group, a sulfophenyl group, asulfonatophenyl group, a sulfamoylphenyl group, anN-ethylsulfamoylphenyl group, an N,N-dipropylsulfamoylphenyl group, anN-tolylsulfamoylphenyl group, anN-methyl-N-(phosphonophenyl)-sulfamoylphenyl group, a phosphonophenylgroup, a phosphonatophenyl group, a diethylphosphonophenyl group, adiphenylphosphonophenyl group, a methylphosphonophenyl group, amethylphosphonatophenyl group, a tolylphosphonophenyl group, atolylphosphonatophenyl group, an allyl group, a 1-propenylmethyl group,2-butenyl group, a 2-methylallylphenyl group, a 2-methylpropenylphenylgroup, a 2-propenylphenyl group, a 2-butynylphenyl group and a3-butynylphenyl group.

The substituted carbonyl group (R¹² --CO--) includes those where R¹² isa monovalent nonmetallic atom group. Preferred examples of thesubstituted carbonyl group include a formyl group, an acyl group, acarboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, acarbamoyl group, an N-alkylcarbamoyl group, an N,N-dialkylcarbamoylgroup, an N-arylcarbamoyl group, an N,N-diarylcarbamoyl group and anN-alkyl-N-arylcarbamoyl group. The alkyl group and the aryl group inthese groups include those described above for the alkyl group and thesubstituted alkyl group and those for the aryl group and the substitutedaryl group, respectively. Among these, more preferred are a formylgroup, an acyl group, a carboxyl group, an alkoxycarbonyl group, anaryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl group, anN,N-dialkylcarbamoyl group and an N-arylcarbamoyl group, still morepreferred are a formyl group, an acyl group, a carboxyl group, analkoxycarbonyl group and an aryloxycarbonyl group. Specific examples ofpreferred substituents include a formyl group, an acetyl group, abenzoyl group, a carboxyl group, a methoxycarbonyl group, anallyloxycarbonyl group, an N-methylcarbamoyl group, an N-phenylcarbamoylgroup, an N,N-diethylcarbamoyl group and a morpholinocarbonyl group.

Among the above-described examples of R, more preferred are a halogenatom (--Cl, --Br), an alkyl group, a substituted alkyl group, an arylgroup, a substituted aryl group and a substituted carbonyl group andstill more preferred are an alkyl group, a substituted alkyl group, anaryl group and a substituted aryl group.

The groups represented by R¹ and R² in formula (I) are described below.The alkyl group, the substituted alkyl group, the aryl group or thesubstituted aryl group include those described above for the groupsrepresented by R. Preferred examples of the groups represented by R¹ andR² include a methyl group, an ethyl group, a propyl group, a butylgroup, a pentyl group, a hexyl group, a 2-ethylhexyl group, a2-chloroethyl group, a 2-hydroxyethyl group, a 2-bromoethyl group, amethoxycarbonylmethyl group, an ethoxycarbonylmethyl group, a phenylgroup, a phenoxyethyl group, a 2-methoxyethyl group and a 2-ethoxyethylgroup.

The groups represented by R³, R⁴, R⁵ and R⁶ in formula (I) are describedbelow. The alkyl group and the substituted alkyl group include thosedescribed above for the groups represented by R.

The substituted oxy group (R¹³ O--) includes those where R¹³ is amonovalent nonmetallic atom group exclusive of hydrogen. Preferredexamples of the substituted oxy group include an alkoxy group, anaryloxy group, an acyloxy group, a carbamoyloxy group, anN-alkylcarbamoyloxy group, an N19-arylcarbamoyloxy group, anN,N-dialkylcarbamoyloxy group, an N,N-diarylcarbamoyloxy group, anN-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxygroup, a phosphonoxy group and a phosphonatoxy group. The alkyl groupand the aryl group in these groups include those described above for thealkyl group and the substituted alkyl group and those for the aryl groupand the substituted aryl group, respectively. The acyl group (R¹¹ CO--)in the acyloxy group include those where R¹¹ is the above-describedalkyl group, substituted alkyl group, aryl group or substituted arylgroup described above. Among these substituents, more preferred are analkoxy group, an aryloxy group, an acyloxy group and an arylsulfoxygroup. Preferred specific examples of the substituted oxy group includea methoxy group, an ethoxy group, a propyloxy group, an isopropyloxygroup, a butyloxy group, a pentyloxy group, a hexyloxy group, adodecyloxy group, a benzyloxy group, an allyloxy group, a phenethyloxygroup, a carboxyethyloxy group, a methoxycarbonylethyloxy group, anethoxycarbonylethyloxy group, a methoxyethoxy group, a phenoxyethoxygroup, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, amorpholinoethoxy group, a morpholinopropyloxy group, anallyloxyethoxyethoxy group, a phenoxy group, a tolyloxy group, axylyloxy group, a mesityloxy group, a cumenyloxy group, amethoxyphenyloxy group, an ethoxyphenyloxy group, a chlorophenyloxygroup, a bromophenyloxy group, an acetyloxy group, a benzoyloxy group, anaphthyloxy group, a phenylsulfonyloxy group, a phosphonoxy group and aphosphonatoxy group.

The substituted thio.group (R¹⁴ S--) includes those where R¹⁴ is amonovalent nonmetallic atom group exclusive of hydrogen. Preferredexamples of the substituted thio group include an alkylthio group, anarylthio group, an alkyldithio group, an aryldithio group and anacylthio group. The alkyl group and the aryl group in these groupsinclude those described above for the alkyl group and the substitutedalkyl group and those for the aryl group and the substituted aryl group,respectively. R¹¹ of the acyl group (R¹¹ CO--) in the acylthio group isthe same as described above. Among these, an alkylthio group and anarylthio group are more preferred. Preferred specific examples of thesubstituted thio group include a methylthio group, an ethylthio group, aphenylthio group, an ethoxyethylthio group, a carboxyethylthio group anda methoxycarbonylthio group.

The ring formed by combining R¹ and R³ or R² and R⁵ with each other isdescribed below. The aliphatic ring formed by combining R¹ and R³ or R²and R⁵ with each other include 5-, 6-, 7- and 8-membered aliphaticrings, with 5- and 6-membered aliphatic rings being preferred. The ringmay have further a substituent on the carbon atom constituting the ring(examples of the substituent include those described above as examplesof the alkyl group and of the substituent on the substituted alkylgroup), or a part of the carbon atoms constituting the ring may bereplaced by a hetero atom (e.g., oxygen, sulfur, nitrogen).

The groups represented by R⁷, R⁸, R⁹ and R¹⁰ in formula (I) aredescribed below. The alkyl group, the substituted alkyl group, the arylgroup, the substituted aryl group, the halogen atom, the substituted oxygroup, the substituted thio group and the substituted carbonyl groupinclude those described above for the groups represented by R, R¹, R²,R³, R⁴, R⁵ and R⁶.

The substituted amino group (R¹⁵ NH--, (R¹⁶)(R¹⁷)N--) includes thosewhere R¹⁵, R¹⁶ and R¹⁷ are each a monovalent nonmetallic atom groupexclusive of hydrogen. Preferred examples of the substituted amino groupinclude an N-alkylamino group, an N,N-dialkylamino group, an N-arylaminogroup, an N,N-diarylamino group, an N-alkyl-N-arylamino group, anacylamino group, an N-alkylacylamino group, an N-arylacylamino group, aureido group, an N'-alkylureido group, an N',N'-dialkylureido group, anN'-arylureido group, an N',N'-diarylureido group, anN'-alkyl-N'-arylureido group, an N-alkylureido group, an N-arylureidogroup, an N'-alkyl-N-alkylureido group, an N'-alkyl-N-arylureido group,an N',N'-dialkyl-N-alkylureido group, an N',N'-dialkyl-N-arylureidogroup, an N'-aryl-N-alkylureido group, an N'-aryl-N-arylureido group, anN',N'-diaryl-N-alkylureido group, an N',N'-diaryl-N-arylureido group, anN'-alkyl-N'-aryl-N-alkylureido group, an N'-alkyl-N'-aryl-N-arylureidogroup, an alkoxycarbonylamino group, an aryloxycarbonylamino group, anN-alkylalkoxycarbonylamino group, an N-alkylaryloxycarbonylamino group,an N-arylalkoxycarbonylamino group and an N-arylaryloxycarbonylaminogroup. The alkyl group and the aryl group in these groups include thosedescribed above for the alkyl group and the substituted alkyl group andthose for the aryl group and the substituted aryl group, respectively,and R^(1l) of the acyl group (R¹¹ CO--) in the acylamino group, theN-alkylacylamino group and the N-arylacylamino group is the same asdescribed above. Among these, more preferred are an N-alkylamino group,an N,N-dialkylamino group, an N-arylamino group and an acylamino group.Preferred specific examples of the substituted amino group include amethylamino group, an ethylamino group, a diethylamino group, amorpholino group, a piperidino group, a pyrrolidino group, a phenylaminogroup, a benzoylamino group and an acetylamino group.

The substituted sulfonyl group (R¹⁸ --SO₂ --) include those where R¹⁸ isa monovalent nonmetallic atom group. More preferred examples thereofinclude an alkylsulfonyl group and an arylsulfonyl group. The alkylgroup and the aryl group in these groups include those described abovefor the alkyl group and the substituted alkyl group and those for thearyl group and the substituted aryl group, respectively. Specificexamples of the substituted sulfonyl group include a butylsulfonyl groupand a chlorophenylsulfonyl group.

The ring formed by combining R⁷ and R⁸, R⁸ and R⁹ or R⁹ and R¹⁰ witheach other is described below. The aliphatic ring formed by combining R⁷and R⁸, R⁸ and R⁹ or R⁹ and R¹⁰ with each other includes 5-, 6-, 7- and8-membered aliphatic rings, with 5- and 6-membered aliphatic-rings beingpreferred. The ring may have further a substituent on the carbon atomsconstituting the ring (examples of the substituent include thosedescribed above as examples of the alkyl group and of the substituent onthe substituted alkyl group), or a part of the carbon atoms constitutingthe ring may be replaced by a hetero atom (e.g., oxygen, sulfur,nitrogen).

Preferred specific examples thereof include those capable of forming abenzocyclopentene ring, a benzocyclohexene ring, a benzocycloheptenering, a benzocyclooctene ring, a 1,3-benzocyclohexadiene ring,1,3-dihydro-1,3-dioxaindene ring or a durolidine ring in cooperationwith the benzene ring containing the carbon atoms to which the groupsare bonded in formula (I).

Most preferred specific examples of the compound represented by formula(I) are set forth below.

                                                                                     -                                                                              ##STR3##                                                                       R R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8             R.sup.9 R.sup.10 m                                                              (a-1) CH.sub.3 CH.sub.3 CH.sub.3 H H H H H H H H 0                             (a-2) CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H H H H H H H H 0                      (a-3) CH.sub.3 C.sub.2 H.sub.4 Cl C.sub.2 H.sub.4 Cl H H H H H H       H H 0                                                                           (a-4) CH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 H H        H H H H H H 0                                                                   (a-5) CH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3        H H H H H H H H 0                                                               (a-6) CH.sub.3 C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5 C.sub.2 H.sub.4             OCOC.sub.2                                                                      H.sub.5 H H H H H H H H 0                                      (a-7)          C.sub.2 H.sub.5 C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 H H        H H H H H H 0                                                                   (a-8) Ph C.sub.2 H.sub.5 C.sub.2                                               H.sub.5 H H H H H H H H 0               (a-9) Ph CH.sub.3 CH.sub.3            CH.sub.3 H H H H H H H 0                                                        (a-10) Ph C.sub.2 H.sub.5 C.sub.2 H.sub.5 H CH.sub.3 H H H H H H 0                  (a-11) Ph C.sub.2 H.sub.5 C.sub.2 H.sub.5 H OCH.sub.3 H H H H H H         (a-12) C.sub.2 H.sub.5 C.sub.2 H.sub.4 Cl C.sub.2 H.sub.4 Cl H H H H Br       H H CH.sub.3 0                                                                  (a-13) CH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 H H       H H OCH.sub.3 H OCH.sub.3 OCH.sub.3 0                                           (a-14) CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H H H H OC.sub.2              H.sub.5 H OC.sub.2 H.sub.5 OC.sub.2                                             H.sub.5 0                             (a-15) CH.sub.3 C.sub.2 H.sub.5         C.sub.2                                                                         H.sub.5 H H H H CH.sub.3 H H Br 0                                             (a-16) CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H H H H H OCH.sub.3            OCH.sub.3 OCH.sub.3 0                                                           (a-17) C.sub.6 H.sub.4CF.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H              CH.sub.3 H H CH.sub.3 H H Br 0                                                  (a-18) Ph C.sub.2 H.sub.5 C.sub.2                                              H.sub.5 H H H OH H H H H 0             (a-19) Ph CH.sub.3 CH.sub.3            CH.sub.3 H H OH H H H H 0                                                       (a-20) CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H H H H H H H H 1                    (a-21) CH.sub.3 C.sub.2 H.sub.4 Cl C.sub.2 H.sub.4 Cl H CH.sub.3        H H H H H H 1                                                                   (a-22) Ph C.sub.2 H.sub.5 C.sub.2 H.sub.5 H H H H OCH.sub.3 H OCH.sub.3 O     CH.sub.3 1                                                                      (a-23) Ph C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 H H H H         Br H H CH.sub.3 1                                                               (a-24) Ph C.sub.2 H.sub.5 C.sub.2 H.sub.5 H H H H CH.sub.3 H H Br             1                                                                              Ph represents a phenyl group.                                             

    __________________________________________________________________________     ##STR4##                                                                         R      R.sup.4                                                                           R.sup.6                                                                         R.sup.7                                                                            R.sup.8                                                                            R.sup.9                                                                            R.sup.10                                                                           m                                        __________________________________________________________________________    (a-25)                                                                            CH.sub.3                                                                             H   H H    H    H    H    0                                        (a-26)                                                                            CH.sub.3                                                                             H   H Br   H    H    CH.sub.3                                                                           0                                        (a-27)                                                                            CH.sub.3                                                                             H   H CH.sub.3                                                                           H    H    Br   0                                        (a-28)                                                                            CH.sub.3                                                                             H   H OCH.sub.3                                                                          H    OCH.sub.3                                                                          OCH.sub.3                                                                          0                                        (a-29)                                                                            CH.sub.3                                                                             H   H H    OCH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3                                                                          0                                        (a-30)                                                                            CH.sub.3                                                                             H   H H    OCH.sub.3                                                                          OCH.sub.3                                                                          H    0                                        (a-31)                                                                            Ph     H   H H    H    H    H    0                                        (a-32)                                                                            Ph     H   H Br   H    H    CH.sub.3                                                                           0                                        (a-33)                                                                            Ph     H   H CH.sub.3                                                                           H    H    Br   0                                        (a-34)                                                                            Ph     H   H OCH.sub.3                                                                          H    OCH.sub.3                                                                          OCH.sub.3                                                                          0                                        (a-35)                                                                            Ph     H   H H    OCH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3                                                                          0                                        (a-36)                                                                            Ph     H   H H    OCH.sub.3                                                                          OCH.sub.3                                                                          H    0                                        (a-37)                                                                            C.sub.2 H.sub.5                                                                      H   H H    H    H    H    0                                        (a-38)                                                                            C.sub.6 H.sub.4CF.sub.3                                                              H   H H    H    H    H    0                                        (a-39)                                                                            CH.sub.3                                                                             H   H H    H    H    H    1                                        (a-40)                                                                            CH.sub.3                                                                             H   H CH.sub.3                                                                           H    H    Br   1                                        (a-41)                                                                            Ph     H   H H    H    H    H    1                                        (a-42)                                                                            Ph     H   H OCH.sub.3                                                                          H    OCH.sub.3                                                                          OCH.sub.3                                                                          1                                        (a-43)                                                                            Ph     H   H H    OCH.sub.3                                                                          OCH.sub.3                                                                          H    1                                        (a-44)                                                                            C.sub.6 H.sub.4CF.sub.3                                                              H   H H    H    H    H    1                                        (a-45)                                                                            CH.sub.3                                                                             OH  H H    H    H    H    0                                        (a-46)                                                                            CH.sub.3                                                                             OH  H CH.sub.3                                                                           H    H    Br   1                                        __________________________________________________________________________    Ph represents a phenyl group                                                   ##STR5##                                                                      ##STR6##                                                                      ##STR7##                                                                      ##STR8##                                                                      ##STR9##                                                                      ##STR10##                                                                      The compound represented by formula (I) can be synthesized according to     a usual method, More specifically, Compound (a- 1) can be obtained by         condensing 4-(N,N-dimethylamino) benzaldehyde with 3-methyl-1-indanone        under the basic condition. The base used in this case may be a commonly       used base and, for example, an alkali metal hydroxide (e.g., caustic          potash, caustic soda) may be suitably used but the base is not limited        thereto. Further, the synthesis method of the compound represented by     

The compounds represented by formula (I) of the present invention can besuitably used alone or in combination of two or more thereof.

The component (iii) for use in the present invention is described belowin detail. The compound as component (iii) of the present invention maybe any as long as it produces an active radical upon light irradiationin the presence of component (ii) together. More specifically, acompound which produces an active radical through an interaction (e.g.,energy transfer, electron transfer, production of excited complex) withcomponent (ii) excited by the light irradiation can be suitably used.Examples of preferred activators include (a) a compound having a carbonhalogen bond, (b) an aromatic onium salt compound, (c) an organicperoxide compound, (d) a thio compound, (e) a hexaarylbiimidazolecompound, (f) a ketooxime ester compound, (g) a borate compound, (h) anazinium compound, (i) a metallocene compound and (j) an active estercompound.

Preferred examples of the compound having a carbon halogen bond as oneexample of component (iii) include those represented by the followingformulae (II), (III), (IV), (V), (VI), (VII) and (VIII):

a compound represented by formula (II): ##STR11## wherein X represents ahalogen atom; Y¹ represents --CX'3, --NH₂, --NHR', --NR'₂ or --OR', inwhich R' represents an alkyl group, a substituted alkyl group, an arylgroup or a substituted aryl group; and R¹⁹ represents --CX₃, an alkylgroup, a substituted alkyl group, an aryl group, a substituted arylgroup or a substituted alkenyl group;

a compound represented by formula (III): ##STR12## wherein R²⁰represents an alkyl group, a substituted alkyl group, an alkenyl group,a substituted alkenyl group, an aryl group, a substituted aryl group, ahalogen atom, an alkoxy group, a substituted alkoxy group, a nitro groupor a cyano group; X' represents a halogen atom; and n represents aninteger of from 1 to 3;

a compound represented by formula (IV):

    R.sup.21 --Z--CH.sub.(n-1) X".sub.m --R.sup.22             (IV)

wherein R²¹ represents an aryl group or a substituted aryl group; andR²² represents --C(═O)--NR²³ R²⁴, --C(═S)NR²³ R²⁴, ##STR13## or ahalogen, in which Z represents --C(═O)--, --C(═S)--or --SO₂ --; R²³ andR²⁴ each represents an alkyl group, a substituted alkyl group, analkenyl group, a substituted alkenyl group, an aryl group or asubstituted aryl group; and R²⁵ has the same meaning as R¹⁹ in formula(II); X" represents a halogen atom; and n represents 1 or 2;

a compound represented by formula (V): ##STR14## wherein R²⁶ representsan aryl or heterocyclic group which may be substituted; R²⁷ represents atrihaloalkyl or trihaloalkenyl group having from 1 to 3 carbon atoms;and p represents 1, 2 or 3;

a carbonylmethylene heterocyclic compound having a trihalogenomethylgroup represented by formula (VI): ##STR15## wherein L represents ahydrogen atom or a substituent represented by formula: CO--(R²⁸)_(q)(CX₃)_(r) ; Q represents a sulfur atom, a selenium atom, an oxygen atom,a dialkylmethylene group, an alken-1,2-ylene group, 1,2-phenylene groupor an N--R group; M represents a substituted or unsubstituted alkyleneor alkenylene group or a 1,2-arylene group; R²⁹ represents an alkylgroup, an aralkyl group or an alkoxyalkyl group; R²⁸ represents acarbocyclic or heterocyclic divalent aromatic group; X represents achlorine atom, a bromine atom or an iodine atom; and q=0 and r=1, or q=1and r=1 or 2;

a 4-halogeno-5-(halogenomethylphenyl)oxazole derivative represented byformula (VII): ##STR16## wherein X represents a halogen atom; trepresents an integer of from 1 to 3; s represents an integer of from 1to 4; R³⁰ represents a hydrogen atom or a CH_(3-t) X_(t) group; and R³¹represents an s-valent unsaturated organic group which may besubstituted; and

a 2-(halogenomethylphenyl)-4-halogenooxazole derivative represented byformula (VIII): ##STR17## wherein X' represents a halogen atom; vrepresents an integer of from 1 to 3; u represents an integer of from 1to 4; R³² represents a hydrogen atom or a CH_(3-v) X_(v) group; and R³³represents a u-valent unsaturated organic group which may besubstituted.

Specific examples of the compound having a carbon-halogen bond include:

compounds described, for example, in Wakabayashi et al., Bull. Chem.Soc. Japan, Vol. 42, p. 2924 (1969), such as 2-phenyl-4,6-bis(trichloromethyl)-S-triazine,2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-S-triazine,2-(p-tolyl)-4,6-bis(trichloromethyl)-S-triazine,2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine,2-(2',4'-dichlorophenyl)-4,6-bis(trichloromethyl)-S-triazine,2,4,6-tris(trichloromethyl)-S-triazine,2-methyl-4,6-bis(trichloromethyl)-S-triazine,2-n-nonyl-4,6-bis(trichloromethyl)-S-triazine and2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-S-triazine;

compounds described in British Pat. No. 1,388,492 such as2-styryl-4,6-bis(trichloromethyl)-S-triazine,2-(p-methylstyryl)-4,6-bis(trichloromethyl)-S-triazine,2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-S-triazine and2-(p-methoxystyryl)-4-amino-6-trichloromethyl-S-triazine;

compounds described in JP-A-53-133428 such as2-(4-methoxynaphtho-1-yl)-4,6-bis-trichloromethyl-S-triazine,2-(4-ethoxynaphtho-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-4-(2-ethoxyethyl)naphtho-1-yl!-4,6-bis-trichloromethyl-S-triazine,2-(4,7-dimethoxynaphtho-1-yl)-4,6-bis-trichloromethyl-S-triazine and2-(acenaphtho-5-yl)-4,6-bis-trichloromethyl-S-triazine;

compounds described in German Patent No. 3,337,024 such as: ##STR18##compounds shown below: ##STR19## compounds described in F. C. Schaeferet al., J. Org. Chem., Vol. 29, p. 1527 (1964) such as2-methyl-4,6-bis(tribromomethyl)-S-triazine,2,4,6-tris(tribromomethyl)-S-triazine,2,4,5-tris(dibromomethyl)-S-triazine,2-amino-4-methyl-6-tribromomethyl-S-triazine and2-methoxy-4-methyl-6-trichloromethyl-S-triazine;

compounds described in JP-A-62-58241: ##STR20## compounds described inJP-A-5-281728: ##STR21## compounds described below which can be easilysynthesized by a person skilled in the art according to the synthesismethod described in M. P. Hutt, E. F. Elslager and L. M. Merbel, Journalof Heterocyclic Chemistry, Vol. 7 (No. 3), page 511 et seq (1970):##STR22## compounds described below: ##STR23## compounds described inGerman Patent No. 2,641,100 such as4-(4-methoxystyryl)-6-(3,3,3-trichloropropenyl)-2-pyrone and4-(3,4,5-trimethoxystyryl)-6-trichloromethyl-2-pyrone;

compounds described in German Patent No. 3,333,450:

    ______________________________________                                         ##STR24##                                                                    (Q = S; R.sup.28 = a benzene ring)                                            R.sup.29    M             L      a    (CX'.sub.3).sub.b                       ______________________________________                                        1    C.sub.2 H.sub.5                                                                          1,2-phenylene H    1    4-CCl.sub.3                           2    CH.sub.2 C.sub.6 H.sub.5                                                                 1,2-phenylene H    1    4-CCl.sub.3                           3    C.sub.2 H.sub.5                                                                          1,2-phenylene H    1    3-CCl.sub.3                           4    C.sub.2 H.sub.5                                                                          1,2-phenylene H    1    4-CF.sub.3                            5    C.sub.2 H.sub.5                                                                          5-CH.sub.3 -1,2-phenylene                                                                   H    0    CCl.sub.3                             6    CH.sub.2 C.sub.6 H.sub.5                                                                 1,2-phenylene H    0    CCl.sub.3                             7    C.sub.2 H.sub.4 OCH.sub.3                                                                1,2-phenylene H    1    4-CCl.sub.3                           ______________________________________                                    

compounds described in German Patent No. 3,021,590:

    __________________________________________________________________________     ##STR25##                                                                                 R.sup.34      X'                                                 __________________________________________________________________________                  ##STR26##    Cl                                                 2                                                                                           ##STR27##    Cl                                                 3                                                                                           ##STR28##    Cl                                                 __________________________________________________________________________     ##STR29##                                                                     ##STR30##                                                                      and, compounds described in German Patent No. 3,021,599:                      #STR31##                                                                      #STR32##                                                                      #STR33##                                                                     ##STR34##                                                                      The aromatic onium salt as another example of component (iii) includes      an aromatic onium salt of the elements belonging to Groups V, VI and VII      of the Periodic Table, specifically, N, P, As, Sb, Bi, O, S, Se, Te and       I. Examples of the aromatic onium salt include the compounds described in     JP-B-52-14277, JP-B-52-14278 and JP-B-52-14279. Specific examples thereof     include the following compounds.                                                #STR35##                                                                      #STR36##                                                                      #STR37##                                                                      #STR38##                                                                      #STR39##                                                                      #STR40##                                                                      #STR41##                                                                      #STR42##                                                                     ##STR43##                                                                      #STR44##                                                                      #STR45##                                                                      #STR46##                                                                      #STR47##                                                                      #STR48##                                                                      #STR49##                                                                      #STR50##                                                                      #STR51##                                                                      #STR52##                                                                      #STR53##                                                                      #STR54##                                                                      #STR55##                                                                      #STR56##                                                                      #STR57##                                                                      #STR58##                                                                      #STR59##                                                                      #STR60##                                                                     ##STR61##                                                                      The organic peroxide as still another example of component (iii) for        use in the present invention includes almost all organic compounds having     one or more oxygen-oxygen bonds per molecule and examples thereof include     methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclo    hexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide,      1,1-bis (tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis                (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy)butane,             tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene            hydroperoxide, paramethane hydroperoxide, 2,5-dimethylhexane-2,5-dihydrope    roxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide,       tert-butylcumyl peroxide, dicumyl peroxide, bis (tert-butylperokyisopropyl    )benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-oxanoyl          peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl            peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate,               di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate,        dimethoxyisopropyl peroxycarbonate, di(3-methyl-3-methoxybutyl)               peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate,       tert-butyl peroxyneodecanoate, tert-butyl peroxyoctanoate, tert-butyl         peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tertiary           carbonate, 3,3',4,4'-tetra-(t-butylperoxycarbonyl)-benzophenone,              3,3',4,4'tetra-(t-aminoperoxycarbonyl)-benzophenone, 3,3',4,4'-tetra-(t-he    xylperoxycarbonyl)-benzophenone, 3,3',4,4'-tetra(t-octylperoxycarbonyl)-be    nzophenone, 3,3',4,4'-tetra(cumylperoxycarbonyl)benzophenone,                 3,3',4,4'-tetra(p-isopropylcumylperoxycarbonyl)benzophenone,                  carbonyldi(t-butylperoxy dihydrogen diphthalate) and carbonyldi(t-hexylper

Among these, preferred are peroxide esters such as3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone,3,3',4,4'-tetra(t-aminoperoxycarbonyl)benzophenone,3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone,3,3',4,4'-tetra(t-octylperoxycarbonyl)benzophenone,3,3',4,4'-tetra(cumylperoxycarbonyl)benzophenone,3,3',4,4'-tetra(p-isopropylcumylperoxycarbonyl)benzophenone anddi-t-butyl diperoxyisophthalate.

The thio compound as an example of component (iii) for use in thepresent invention is represented by the following formula (IX):##STR62## wherein R³⁵ represents an alkyl group, an aryl group or asubstituted aryl group; R³⁶ represents a hydrogen atom or an alkylgroup, and R³⁵ and R³⁶ may be combined with each other to represent anonmetallic atom group necessary for forming a 5-, 6- or 7-membered ringwhich may contain a hetero atom selected from an oxygen atom, a sulfuratom and a nitrogen atom.

The alkyl group represented by R³⁵ in formula (IX) is preferably analkyl group having from 1 to 4 carbon atoms. The aryl group representedby R¹⁶ is preferably an aryl group having from 6 to 10 carbon atoms suchas phenyl and naphthyl and the substituted aryl group includes theabove-described aryl group substituted with a halogen atom such aschlorine, an alkyl group such as methyl or an alkoxy group such asmethoxy or ethoxy. R³⁶ is preferably an alkyl group having from 1 to 4carbon atoms.

Specific examples of the thio compound represented by formula (IX)include the following compounds.

    ______________________________________                                        No.           R.sup.35       R.sup.36                                         ______________________________________                                         1            H              H                                                 2            H              CH.sub.3                                          3            CH.sub.3       H                                                 4            CH.sub.3       CH.sub.3                                          5            C.sub.6 H.sub.5                                                                              C.sub.2 H.sub.5                                   6            C.sub.6 H.sub.5                                                                              C.sub.4 H.sub.9                                   7            C.sub.6 H.sub.4 Cl                                                                           CH.sub.3                                          8            C.sub.6 H.sub.4 Cl                                                                           C.sub.4 H.sub.9                                   9            C.sub.6 H.sub.4CH.sub.3                                                                      C.sub.4 H.sub.9                                  10            C.sub.6 H.sub.4OCH.sub.3                                                                     CH.sub.3                                         11            C.sub.6 H.sub.4OCH.sub.3                                                                     C.sub.2 H.sub.5                                  12            C.sub.6 H.sub.4 OC.sub.2 H.sub.5                                                             CH.sub.3                                         13            C.sub.6 H.sub.4 OC.sub.2 H.sub.5                                                             C.sub.2 H.sub.5                                  14            C.sub.6 H.sub.4 OCH.sub.3                                                                    C.sub.4 H.sub.9                                  15            (CH.sub.2 ) .sub.2                                              16            (CH.sub..sub.2 ) .sub.2S                                        17            CH(CH.sub.3)CH.sub.2S                                           18            CH.sub.2CH(CH.sub.3)S                                           19            C(CH.sub.3).sub.2CH.sub.3S                                      20            CH.sub.2C(CH.sub.3).sub.2S                                      21            (CH.sub.2 ) .sub.2O                                             22            CH(CH.sub.3)CH.sub.2O                                           23            C(CH.sub.3).sub.2CH.sub.2O                                      24            CHCHN(CH.sub.3)                                                 25            (CH.sub.2 ) .sub.3S                                             26            (CH.sub.2 ) .sub.2CH(CH.sub.3)S                                 27            (CH.sub.2 ) .sub.3O                                             28            (CH.sub.2 ) .sub.5                                              29            C.sub.6 H.sub.4O                                                30            NC(SCH.sub.3)S                                                  31            C.sub.6 H.sub.4NH                                               32                                                                                           ##STR63##                                                      ______________________________________                                    

The hexaarylbiimidazole as another example of component (iii) for use inthe present invention includes2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole,2,2'-bis(o-bromophenyl)-4,4',5,5'-tetraphenylbiimidazole,2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole,2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra (m-methoxyphenyl)-biimidazole,2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole,2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole,2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole and2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

The ketooxime ester as another example of component (iii) for use in thepresent invention includes 3-benzoyloxyiminobutan-2-one,3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one,2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one,2-benzoyloxyimino-1-phenylpropan-1-one,3-p-toluenesulfonyloxyiminobutan-2-one and2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

The borate salt as still another example of component (iii) of thepresent invention includes the compounds represented by the followingformula (X): ##STR64## wherein R³⁷, R³⁸, R³⁹ and R⁴⁰, which may be thesame or different, each represents a substituted or unsubstituted alkylgroup, a substituted or unsubstituted aryl group, a substituted orunsubstituted alkenyl group, a substituted or unsubstituted alkynylgroup or a substituted or unsubstituted heterocyclic group, two or moregroups of R³⁷, R³⁸, R³⁹ and R⁴⁰ may be combined to form a cyclicstructure, provided that at least one of R³⁷, R³⁸, R³⁹ and R⁴⁰ is asubstituted or unsubstituted alkyl group; and Z⁺ represents an alkalimetal cation or a quaternary ammonium cation).

The alkyl group represented by R³⁷ to R⁴⁰ includes linear, branched andcyclic alkyl groups each preferably having from 1 to 18 carbon atoms.Specific examples thereof include methyl, ethyl, propyl, isopropyl,butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl andcyclohexyl. The substituted alkyl group includes the above-describedalkyl group having a substituent such as a halogen atom (e.g., --Cl,Br), a cyano group, a nitro group, an aryl group (preferably a phenylgroup), a hydroxy group, ##STR65## (wherein R⁴¹ and R⁴² eachindependently represents a hydrogen atom, an alkyl group having from 1to 14 carbon atoms or an aryl group), --COOR⁴³ (wherein R⁴³ represents ahydrogen atom, an alkyl group having from 1 to 14 carbon atoms or anaryl group), --OCOR⁴⁴ or --OR⁴⁴ (wherein R⁴⁴ represents an alkyl grouphaving from 1 to 14 carbon atoms or an aryl group).

The aryl group represented by R³⁷ to R⁴⁰ includes a mono-, di- ortri-cyclic aryl group such as phenyl and naphthyl and the substitutedaryl group includes the above-described aryl group which has asubstituent described above for the substituted alkyl group or an alkylgroup having from 1 to 14 carbon atoms.

The alkenyl group represented by R³⁷ to R⁴⁰ includes linear, branchedand cyclic alkenyl groups each having from 2 to 18 carbon atoms and thesubstituent for the substituted alkenyl group includes the substituentsdescribed above for the substituted alkyl group.

The alkynyl group represented by R³⁷ to R⁴⁰ includes linear and branchedalkynyl group each having from 2 to 28 carbon atoms and the substituentof the substituted alkynyl group includes the substituents describedabove for the substituted alkyl group.

The heterocyclic group represented by R³⁷ to R⁴⁰ includes 5- and greatermembered, preferably 5- to 7-membered, heterocyclic groups eachcontaining at least one of N, S and O and the heterocyclic group maycontain a condensed ring and further may have a substituent describedabove for the substituted alkyl group.

Specific examples of the compound represented by formula (X) include thecompounds described in U.S. Pat. Nos. 3,567,453 and 4,343,891 andEuropean Patent Nos. 109,772 and 109,773 and the compounds describedbelow. ##STR66##

Examples of the azinium salt compound as another example of component(iii) of the present invention include the compounds having an N--O bonddescribed in JP-A-63-138345, JP-A-63-142345, JP-A-63-142346,JP-A-63-143537 and JP-B-46-42363. Specific examples of the azinium saltcompound include 1-methoxy-4-phenylpyridinium tetra fluoroborate.

Examples of the metallocene compound as still another example ofcomponent (iii) include various titanocene compounds described inJP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705and JP-A-5-83588. Specific examples thereof includedicyclopentadienyl-Ti-bis-phenyl,dicyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl,dicyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl,dicyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl,dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl,dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl,dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl,dimethylcyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl,dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl anddimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl. Also,the iron-allene complexes described in JP-A-1-304453 and JP-A-1-152109may be suitably used.

Examples of the active ester compound as still another example ofcomponent (iii) include the imidosulfonate compounds described inJP-B-62-6223 and the active sulfonates described in JP-B-63-14340 andJP-A-59-174831.

The compounds as component (iii) of the present invention may be usedindividually or in combination of two or more thereof.

The concentration of the photopolymerization initiation system, namely,component (ii) and component (iii), contained in the composition of thepresent invention is usually low and if it is unduly excessive,disadvantageous results such as cutoff of effective light rays may becaused.

In the present invention, the amount of the photopolymerizationinitiation system is from 0.01 to 60%, preferably from 1 to 30%, basedon the total amount of the photopolymerizable, ethylenically unsaturatedcompound and the linear organic high molecular polymer which is added ifdesired.

With respect to the ratio between component (ii) and component (iii) asthe components in the photopolymerization initiation system used in thepresent invention, component (iii) is preferably used in an amount offrom 0.01 to 50 parts by weight, more preferably from 0.02 to 20 partsby weight, and most preferably from 0.05 to 10 parts by weight, per partby weight of the organic dye as component (ii).

The photopolymerizable composition of the present invention may furthercontain a known compound which acts to increase more the sensitivity orprevent the polymerization inhibition due to oxygen, as a co-sensitizer.

One example of the co-sensitizer includes amines and examples of theamine include the compounds described in M. R. Sander Journal of PolymerSociety, Vol. 10, p. 3173 (1972), JP-B-44-20189, JP-A-51-82102,JP-A-52-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537,JP-A-64-33104 and Research Disclosure, No. 33825. Specific examplesthereof include triethanolamine, ethyl p-dimethylaminobenzoate,p-formyldimethylaniline and p-methylthiodimethylaniline.

Another example of the co-sensitizer includes thiols and sulfides andexamples of the thiol and the sulfide include the thiol compoundsdescribed in JP-A-53-705, JP-B-55-500806 and JP-A-5-142772 and thedisulfide compounds described in JP-A-56-75643. Specific examplesthereof include α-mercaptobenzothiazole, α-mercaptobenzoxazole,α-mercaptobenzimidazole, α-mercapto-4(3H)-quinazoline andβ-mercaptonaphthalene.

Still another example of the co-sensitizer includes amino acid compounds(e.g., N-phenylglycine), organometallic compounds described inJP-B-48-42965 (e.g., tributyltin acetate), hydrogen donors described inJP-B-55-34414, sulfur compounds described in Japanese Pat. No.Application No. 5-91089 (e.g. trithiane), phosphorus compounds describedin JP-A-6-250389 (e.g., diethyl phosphite) and Si--H and Ge--H compoundsdescribed in Japanese Patent No. Application No. 6-191605.

Still another example of the co-sensitizer includes aminoketonecompounds described in U.S. Pat. No. 4,318,791 and European Patent No.Application No. 0284561A1 and examples of the aminoketone compoundinclude the following compounds. ##STR67##

Another example of the co-sensitizer includes oxime ether compoundsdescribed in Japanese Patent No. Application No. 7-13108. Specificexamples of the oxime ether compounds are shown below; however, thepresent invention is not limited thereto. ##STR68##

When the above-described co-sensitizer is used, it is preferred to useit in an amount of from 0.01 to 50 parts by weight, more preferably from0.02 to 20 parts by weight and most preferably from 0.05 to 10 parts byweight, per part by weight of the compound as component (ii).

The photopolymerizable composition of the present invention preferablycontains a linear organic high molecular polymer as a binder. The"linear organic high molecular polymer" may be any linear organic highmolecular polymer as long as it has compatibility with thephotopolymerizable, ethylenically unsaturated compound. Preferably, awater- or alkalescent water-soluble or swellable linear organic highmolecular polymer capable of water development or alkalescent waterdevelopment is selected. The linear organic high molecular polymer isused not only as the film forming agent of the composition but also as adeveloper appropriately selected depending on the use of water,alkalescent water or an organic solvent. For example, when awater-soluble organic high molecular polymer is used, water developmentcan be carried out. This kind of linear organic high molecular polymerincludes an addition polymer having a carboxylic acid group on the sidechain and examples thereof include a methacrylic acid copolymer, anacrylic acid copolymer, an itaconic acid copolymer, a crotonic acidcopolymer, a maleic acid copolymer and a partially esterified maleicacid copolymer described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577,JP-B-54-25957, JP-A-54-92723, JP-A-59-53836 and JP-A-59-71048. Further,an acidic cellulose derivative having a carboxylic acid group on theside chain may be included. An addition product of a cyclic acidanhydride to the addition polymer having a hydroxyl group may also beuseful. Among these, a benzyl (meth)acrylate/(meth)acrylic acid/otheraddition polymerizable vinyl monomer, if desired! copolymer and an allyl(meth)acrylate/(meth)acrylic acid/other addition polymerizable vinylmonomer, if desired! copolymer are preferred. In addition, polyvinylpyrrolidone and polyethylene oxide are useful as a water-soluble linearorganic polymer. Further, an alcohol-soluble polyamide and a polyetherof 2,2-bis(4-hydroxyphenyl)propane with epichlorohydrin are also usefulso as to increase the strength. of the cured film. The above-describedlinear organic high molecular polymer can be mixed into the entirecomposition in any amount. However, if the mixing amount exceeds 90 wt%, disadvantageous results may be caused in view of the strength of animage formed and the like. The mixing amount is preferably from 30 to85%. The weight ratio of the photopolymerizable, ethylenicallyunsaturated compound to the linear organic high molecular polymer ispreferably from 1/9 to 7/3, more preferably from 3/7 to 5/5.

In the present invention, other than the above-described fundamentalcomponents, a slight amount of a thermal polymerization inhibitor ispreferably added so as to prevent unnecessary thermal polymerization ofthe polymerizable, ethylenically unsaturated compound during theproduction or storage of the photosensitive composition. Examples ofsuitable thermal polymerization inhibitors include hydroquinone,p-methoxyphenol,di-t-butyl-p-cresol, pyrogallol, t-butylcatechol,benzoquinone, 4,4'-thiobis(3-methyl-6-t-butylphenol),2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamineprimary cerium salt and N-nitrosophenylhydroxylamine aluminum salt. Theaddition amount of the thermal polymerization inhibitor is preferablyfrom about 0.01 to about 5% based on the weight of the entirecomposition. Also, if desired, a higher fatty acid derivative such as abehenic acid and a behenic acid amide may be added to disperse unevenlyon the surface of the photosensitive layer during the drying processafter coating so as to prevent the polymerization inhibition due tooxygen. The addition amount of the higher fatty acid derivative ispreferably from about 0.5 to about 10% of the entire composition.

In the present invention, a dye or a pigment may be added for thepurpose of coloring the photosensitive layer. The addition amount of thedye or the pigment is from 0.01 to 20%, preferably from 0.5 to 10% ofthe entire composition. A pigment is preferred more than a dye.

As the pigment, commercially available pigments and known pigmentsdescribed in various publications, for example, in C. I. Binran,"Saishin Gnaryo Binran", Nippon Ganryo Gijutsu Kyokai (compiler) (1977),Saishin Ganryo Oyo Gijutsu, CMC Shuppan (1986) and Insatsu Ink Gijutsu,CMC Shuppan (1984), can be used.

Examples of the pigment include a black pigment, a yellow pigment, anorange pigment, a brown pigment, a red pigment, a violet pigment, a bluepigment, a green pigment, a fluorescent pigment, a metal powder pigmentand in addition, a polymer bonded dye. Specific examples thereof includean insoluble azo pigment, an azo lake pigment, a condensed azo pigment,a chelate azo pigment, a phthalocyanine-based pigment, ananthraquinone-based pigment, a perylene- or perynone-based pigment, athioindigo-based pigment, a quinacridone-based pigment, adioxazine-based pigment, an isoindolinone-based pigment, aquinophthalone-based pigment, a dyed lake pigment, an azine pigment, anitroso pigment, a nitro pigment, a natural pigment, a fluorescentpigment and an inorganic pigment. Among these, preferred are aninsoluble azo pigment, an azo lake pigment, a phthalocyanine-basedpigment and an anthraquinone-based pigment.

The pigment may be dispersed in the presence of a polymer and examplesof the polymer include polymers having an aliphatic double bond on themain chain or on the side chain as represented by formulae (x), (y) and(z) of Japanese Patent No. Application No. 6-193357: ##STR69## whereinR⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰ and R⁵¹ each independently represents ahydrogen atom, an alkyl group or an aryl group; X, Y and Z eachindependently represents a divalent linking group; and Q represents anatomic group necessary for forming an aliphatic ring.

The alkyl group includes an alkyl group preferably having from 1 to 20,more preferably from 1 to 10, most preferably from 1 to 6, carbon atoms(e.g., methyl, ethyl, propyl, butyl, hexyl, isopropyl).

The aryl group includes an aryl group having from 6 to 22 carbon atoms(e.g., phenyl, naphthyl, anthryl).

The alkyl group or the aryl group may be substituted with a substituentsuch as an alkoxy group, an amido group or an alkoxycarbonyl group.

R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰ and R⁵¹ are each preferably a hydrogen atomor an alkyl group, more preferably a hydrogen atom or methyl.

Examples of the divalent linking group represented by X or Y include analkylene group, an arylene group, a carbonyl group, an imino group, anoxygen atom, a sulfur atom or a combination of these. The divalentlinking group may be substituted with an aryl group, a halogen atom, ahydroxyl group or a cyano group.

The alkylene group includes an alkylene group having preferably from 2to 10, more preferably from 2 to 6, still more preferably from 2 or 3,carbon atoms (e.g., --CH₂ CH₂ CH₂ --, --CH₂ CH₂ --, --CH₂ CH(CH₃)--).

The arylene group includes an arylene group having from 6 to 22 carbonatoms (e.g., ##STR70##

X is preferably an alkylene group.

Y is preferably an alkylene group, a carbonyl group, an oxygen atom or acombination of these.

The aliphatic ring formed by Q is preferably an aliphatic ring havingfrom 5 to 30 carbon atoms resulting from combination of 5- or 6-memberedrings (e.g., cyclohexane ring, norbornenyl ring, dicyclopentadienering). The aliphatic ring includes bicyclic or tricyclic hydrocarbonhaving a bridgehead carbon atom. The number of carbon-carbon double bondpresent in the aliphatic ring is preferably one.

The photopolymerizable composition of the present invention may containan inorganic filler or other known additives for improving physicalproperties of the cured film.

Further, a surface active agent is preferably added so as to improve thesurface state on coating.

The photopolymerizable composition of the present invention is dissolvedin various organic solvents and then coated on a support. Examples ofthe solvent include acetone, methyl ethyl ketone, cyclohexane, ethylacetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, ethylene glycoldimethyl ether, propylene glycol monomethyl ether, propylene glycolmonoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol,ethylene glycol monomethyl ether acetate, ethylene glycol ethyl etheracetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutylether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethyleneglycol monomethyl ether, diethylene glycol monoethyl ether, diethyleneglycol dimethyl ether, diethylene glycol diethyl ether, propylene glycolmonomethyl ether acetate, propylene glycol monoethyl ether acetate,3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide,γ-butyrolactone, methyl lactate and ethyl lactate. These solvents may beused individually or in combination. The solid concentration in thecoating solution is suitably from 2 to 50 wt %. The coverage is in termsof the weight after drying preferably from about 0.1 to about 10 g/m²,more preferably from 0.5 to 5 g/m².

As the above-described support, a dimensionally stable, plate-likematerial is used. Examples of the dimensionally stable, plate-likematerial include paper, paper laminated with plastics (e.g.,polyethylene, polypropylene, polystyrene), sheet of a metal such asaluminum (including aluminum alloy), zinc or copper, a plastic film suchas cellulose diacetate, cellulose triacetate, cellulose propionate,cellulose butyrate, cellulose acetate butyrate, cellulose nitrate,polyethylene terephthalate, polyethylene, polystyrene, polypropylene,polycarbonate and polyvinyl acetal, and paper or plastic film laminatedwith or having evaporated thereon the above-described metal. Among thesesupports, an aluminum plate is particularly preferred because it isdimensionally stable to an extreme extent and in addition, cheap. Also,a composite sheet obtained by bonding an aluminum sheet on apolyethylene terephthalate film described in JP-B-48-18327 may bepreferably used.

A support having a metal, particularly an aluminum surface is preferablysubjected to surface treatment such as graining treatment, dippingtreatment in an aqueous solution of sodium silicate, potassiumfluorozirconate or phosphate, or anodic oxidation treatment.

The graining treatment is preferably conducted by brush graining orelectrolysis graining. In the case of electrolysis graining, theelectrolyte is preferably an aqueous solution of nitric acid orhydrochloric acid, more preferably an aqueous solution of nitric acid.

An aluminum plate subjected to graining and then to dipping treatment inan aqueous solution of sodium silicate may be preferably used. Further,an aluminum plate subjected to anodic oxidation treatment and then todipping treatment in an aqueous solution of alkali metal silicatedescribed in JP-B-47-5125 may be also suitably used.

The anodic oxidation treatment is carried out by applying current to thealuminum plate as an anode in an electrolyte, for example, in an aqueousor non-aqueous solution of an inorganic acid such as phosphoric acid,chromic acid, sulfuric acid or boric acid or of an organic acid such asoxalic acid or sulfamic acid, which solutions may be used individuallyor in combination of two or more thereof.

The silicate electrodeposition described in U.S. Pat. No. 3,658,662 isalso effective.

Further, the surface treatment comprising a combination of electrolysisgraining with the above-described anodic oxidation treatment and sodiumsilicate treatment disclosed in JP-B-46-27481, JP-A-52-58602 andJP-A-52-30503 is also useful. In this case, the sodium silicatetreatment may be omitted.

Furthermore, a support may also be suitably subjected to mechanicalgraining, chemical etching, electrolysis graining, anodic oxidationtreatment and sodium silicate treatment successively as disclosed inJP-A-56-28893.

Still further, a support may be suitably subjected, after theabove-described treatments, to undercoating by a water-soluble resinsuch as a polymer or copolymer having a polyvinyl phosphonic acid or asulfonic acid group on the side chain, a polyacrylic acid, awater-soluble metal salt (e.g., zinc borate), or by a yellow dye or anamine salt.

The above-described treatment to achieve hydrophilicity is effected torender the support surface hydrophilic, to prevent harmful reaction ofthe photopolymerizable composition to be coated thereon and to improvethe adhesion property of the photosensitive layer.

Further, the back surface of the support may be preferably subjected tobackcoating described in JP-A-5-2271 and JP-A-6-35174 so as to preventthe elution of aluminum into the developer.

In order to prevent polymerization inhibition action of the oxygen inair, a protective layer comprising a polymer having an excellent oxygencutting property, such as polyvinyl alcohol, in particular, polyvinylalcohol having a saponification degree of 95% or more, or an acidiccellulose, may be provided on the photopolymerizable composition layeron the support. The coating method of the protective layer is describedin detail, for example, in U.S. Pat. No. 3,458,311 and JP-A-55-49729.The coating amount thereof is preferably from 0.1 to 5.0 g/m², morepreferably from 0.5 to 3 g/m².

The photopolymerizable composition of the present invention can be usedfor usual photopolymerization. Further, the composition can be used invarious fields, for example, as a photoresist in producing a printingplate or a printed board. In particular, since the photopolymerizablecomposition of the present invention has such properties as highsensitivity and wide spectral sensitivity extending even to a visiblelight region, the composition can provide good effects when it isapplied to a photosensitive material for a visible light laser such asan Ar⁺ laser or a YAG-SHG laser.

Further, the photopolymerizable composition of the present invention ishighly sensitive and has sensitivity to visible light and therefore, itcan be advantageously used particularly for an image formation systemusing a microcapsule.

The application to the image formation system using a microcapsule isdescribed in,. for example, JP-A-57-197538, JP-A-61-130945,JP-A-58-88739, JP-A-58-88740 and European Patent No. Application No.223,587A1. This image formation method comprises coating a microcapsulecontaining, for example, a photopolymerization initiator compositionconsisting of an ethylenic vinyl compound and a photopolymerizationinitiator and a dye precursor on a support, imagewise exposing theresulting photosensitive sheet to cure microcapsules on the exposedarea, superposing a developer sheet thereon and applying pressurethroughout the sheet to rapture the microcapsules on the unexposed area,whereby a dye image-forming material (e.g., dye precursor) istransferred to an image-receiving element (e.g., developer layer) toform colors.

The photosensitive material using the photopolymerizable composition ofthe present invention may be heated after the imagewise exposure. Theheating temperature is preferably from 60° to 160° C., more preferablyfrom 80° to 130° C. The heating time is preferably from 1 second to 5minutes.

The unexposed area of the photosensitive layer is removed by a developerto obtain an image. In using the photopolymerizable composition forproducing a lithographic printing plate, the developer described inJP-B-57-7427 is preferred and an aqueous solution of an inorganic alkaliagent such as sodium silicate, potassium silicate, sodium hydroxide,potassium hydroxide, lithium hydroxide, sodium tertiary phosphate,sodium secondary phosphate, ammonium tertiary phosphate, ammoniumsecondary phosphate, sodium metasilicate, sodium bicarbonate or aqueousammonia or of an organic alkali agent such as monoethanolamine ordiethanolamine is suitably used. The alkali agent is added to give aconcentration of from 0.1 to 10 wt %, preferably from 0.5 to 5 wt %.

The above-described alkaline aqueous solution may contain, if desired, asurface active agent or an organic solvent such as benzyl alcohol,2-phenoxyethanol or 2-butoxyethanol, in a small amount. Examples thereofinclude those described in U.S. Pat. Nos. 3,375,151 and 3,615,480.Further, the developers described in JP-A-50-26601, JP-A-58-54341,JP-B-56-39464 and JP-B-56-42860 are also excellent.

However, the use of an organic solvent involves a hygienic problem suchas toxicity and odor at the operation site, a safety problem such asfiring, a problem in view of operationability such as generation ofbubbles, or a problem of environmental pollution due to the waste waterand accordingly, the developer preferably contains substantially noorganic solvent. The aqueous alkali developer substantially free of anorganic solvent includes the developer compositions described in, forexample, JP-A-59-84241 and JP-A-57-192952.

A commercially available developer which can be suitably used is asolution obtained by diluting DP-4 (produced by Fuji Photo Film Co.,Ltd.) with water to from 1/6 to 1/30.

The photosensitive lithographic printing plate using thephotopolymerizable composition of the present invention may be subjectedafter development to such treatments as described in JP-A-54-8002,JP-A-55-115045 and JP-A-59-58431, more specifically, degreasingtreatment through or without water washing, treatment with an aqueoussolution containing an acid or degreasing treatment after treatment withan aqueous solution containing an acid. In the development process ofthis kind of photosensitive lithographic printing plate, the aqueousalkali solution is consumed according to the processed amount to causereduction in the alkali concentration or the alkali concentration isreduced due to air in a long-time operation in an automatic developingmachine to lower the processing capability. In this case, the processingcapability can be recovered by the replenishers and the replenishingmethods described in JP-A-54-62004, JP-A-55-22759, JP-A-55-115039,JP-A-56-12645, JP-A-58-95349, JP-A-64-21451, JP-A-1-180548 andJP-A-2-3065.

The above-described print-making process is preferably carried out in anautomatic developing machine described in JP-A-2-7054 and JP-A-2-32357.As the degreasing gum to be coated, if desired, at the final step of theprint-making process, those described in JP-B-62-16834, JP-B-62-25118,JP-B-63-52600, JP-A-62-7595, JP-A-62-11693 and JP-A-62-83194 arepreferably used.

After the development, the printing plate may be subjected to burningheat treatment or post exposure to improve the printing durability atprinting.

The photopolymerizable composition of the present invention exhibitshigh sensitivity to active light rays over a wide region of fromultraviolet light to visible light. Accordingly, an ultrahigh-pressuremercury lamp, a high-pressure mercury lamp, a medium-pressure mercurylamp, a low-pressure mercury lamp, a chemical lamp, a carbon arc lamp, axenon lamp, a metal halide lamp, various laser lamps such as a visiblelaser lamp and an ultraviolet laser lamp, a fluorescent lamp, a tungstenlamp or sunlight can be used as a light source.

The present invention will be described below in greater detail byreferring to the examples, but the present invention should not beconstrued as being limited to these examples. All parts, percents,ratios and the like are based on weight unless otherwise indicated.

SYNTHESIS EXAMPLE 1 (preparation of 3-methyl-1-indanone)

To 31.8 g of aluminum chloride, 6.8 g of crotonic acid and 50.0 ml ofbenzene were added and the mixture was reacted under reflux for 5 hours.After filtering the reaction solution, benzene was removed from thefiltrate by distillation and the residue was distilled in a vacuum(120°-123° C./12 mmHg) to obtain 9.7 g of 3-methyl-1-indanone.

SYNTHESIS EXAMPLE 2 (preparation of Sensitizer (a-1))

4-(N,N-Dimethyl)benzaldehyde (3.0 g), 2.9 g of 3-methyl-1-indanone and0.2 g of sodium hydroxide were reacted in 80 ml of an ethanol solventunder a nitrogen atmosphere at 80° C. for 5 hours. The reaction productwas ice-cooled after adding thereto 25 ml of water to obtain 4.1 g ofcrude Sensitizer (a-1). Further, crude Sensitizer (a-1) wasrecrystallized from ethanol/water to obtain 3.5 g of Sensitizer (a-1).Sensitizer (a-1) was identified by NMR (nuclear magnetic resonance) andinfrared absorption spectrum.

SYNTHESIS METHOD 3 (preparation of Sensitizer (a-25))

Durolidine-9-carbaldehyde (4.0 g) synthesized by a usual method, 3.0 gof 3-methyl-1-indanone and 0.3 g of sodium hydroxide were reacted in 80ml of ethanol under a nitrogen atmosphere at 80° C. for 7 hours. Thereaction product was ice-cooled and allowed to stand over night andthen, crystals deposited were collected by filtration to obtain 5.8 g ofcrude Sensitizer (a-25). Further, crude Sensitizer (a-25) wasrecrystallized from ethanol/water to obtain 5.3 g of Sensitizer (a-25).Sensitizer (a-25) was identified by NMR and infrared absorptionspectrum.

SYNTHESIS EXAMPLE 4(preparation of 3-phenyl-1-indanone)

To 25.0 g of aluminum chloride, 8.5 g of cinnamic acid and 37.5 ml ofbenzene were added and the mixture was reacted under reflux for 5 hours.The reaction solution was processed by a usual method to obtain 5.1 g of3-phenyl-1-indanone.

SYNTHESIS EXAMPLE 5 (preparation of Sensitizer (a-31))

Durolidine-9-carbaldehyde (4.0 g), 4.2 g of 3-phenyl-1-indanone and 0.4g of sodium hydroxide were reacted in 80 ml of ethanol under a nitrogenatmosphere at 80° C. for 7 hours. The reaction product was ice-cooledand allowed to stand over night and crystals deposited were collected byfiltration to obtain 6.5 g of crude Sensitize (a-31). Then, crudeSensitizer (a-31) was recrystallized from ethanol/water to obtain 5.8 gof Sensitizer (a-31). Sensitizer (a-31) was identified by NMR and theinfrared absorption spectrum.

EXAMPLES 1 TO 8

A 0.3 mm-thick aluminum plate was dipped in a 10% sodium hydroxide at60° C. for 25 seconds to effect etching, washed with flowing water,neutralization-washed with a 20% nitric acid and then washed with water.The resulting plate was subjected to electrolysis graining treatmentusing a sinewaveform alternating current in a 1% aqueous nitric acidsolution at an anode electricity quantity of 300 coulomb/dm².Subsequently, the plate was dipped in an aqueous solution of a 1% sodiumhydroxide at 40° C. for 5 seconds and then dipped in an aqueous solutionof a 30% sulfuric acid to effect desmutting at 60° C. for 40 seconds.Thereafter, the plate was subjected to anodic oxidation treatment in anaqueous solution of a 20% sulfuric acid at a current density of 2 A/dm²for 2 minutes to give an anodically oxidized film thickness of 2.7 g/m².The surface roughness measured was 0.3 μm (Ra indication).

The following sol-gel reaction solution was coated on the back surfaceof the thus-treated substrate by a bar coater and dried at 80° C. for 1minute to prepare Support A with a backcoat layer having a coated amountafter drying of 70 mg/m².

    ______________________________________                                        Preparation of Sol-Gel Reaction Solution:                                     ______________________________________                                        Tetraethyl silicate                                                                              50     parts by weight                                     Water              20     parts by weight                                     Methanol           15     parts by weight                                     Phosphoric acid    0.05   part by weight                                      ______________________________________                                    

The above-described components were mixed and stirred and then heatgeneration started in about 5 minutes. After allowing them to react for60 minutes, the following solution was added thereto to prepare acoating solution for the backcoat layer.

    ______________________________________                                        Pyrogallol formaldehyde                                                                           4      parts by weight                                    condensed resin (M.W. 2,000)                                                  Dimethyl phthalate  5      parts by weight                                    Fluorine surface active agent                                                                     0.7    part by weight                                     (N-butyl perfluorooctane                                                      sulfonamidoethylacrylate/                                                     polyoxyethylene acrylate                                                      copolymer, molecular weight:                                                  20,000)                                                                       Methanol silica sol (produced                                                                     50     parts by weight                                    by Nissan Chemical Co., Ltd.,                                                 methanol: 30%)                                                                Methanol            800    parts by weight                                    ______________________________________                                    

The photosensitive composition having the following composition wascoated on the surface of the aluminum plate treated as above to give adry coated weight of 1.5 g/m² and dried at 80° C. for 2 minutes to forma photosensitive layer.

    ______________________________________                                        Pentaerythritol tetraacrylate                                                                          2.0    g                                             Benzyl methacrylate/methacrylic acid                                                                   2.0    g                                             copolymer (copolymerization molar ratio:                                      80/20)                                                                        Component (ii)           X      g                                             Component (iii)          Y      g                                             Fluorine nonionic surface active agent                                                                 0.03   g                                             (F-177, produced by Dai-Nippon Ink &                                          Chemicals, Inc.)                                                              Thermal polymerization inhibitor: N-                                                                   0.01   g                                             nitrosophenylhydroxylamine aluminum salt                                      Pigment Dispersion       2.0    g                                             Composition:                                                                  Copper phthalocyanine    30     parts                                         Benzyl methacrylate/methacrylic                                                                        20     parts                                         acid copolymer (copolymerization                                              molar ratio: 83/17)                                                           Cyclohexanone            35     parts                                         Methoxypropyl acetate    35     parts                                         Propylene glycol monomethyl ether                                                                      80     parts                                         Methyl ethyl ketone      20     g                                             Propylene glycol monomethyl ether                                                                      20     g                                             ______________________________________                                    

The specifications of component (ii) and component (iii) are describedin Table A below.

On the thus-provided photosensitive layer, a 3 wt % aqueous solution ofpolyvinyl alcohol (saponification degree: 98 mol %, polymerizationdegree: 1,000) was coated to give a dry coated weight of 2 g/m² anddried at 100° C. for 2 minutes to form a protective layer.

FUJI PS Step Guide (a gray scale having ΔD=0.15 and discontinuouslychanged in the transmission density, manufactured by Fuji Photo FilmCo., Ltd.) was put into close contact with the photosensitive materialobtained above and light for exposure was irradiated thereon.

The light source used was a xenon lamp and light was irradiated throughKenko Optical Filter BP-53. The energy on the PS Step Guide surface was0.25 mJ/cm².

The exposed photosensitive material was heated at 120° C. for 20 secondsand then developed. The sensitivity was shown by a clear stage numberafter development of the PS Step Guide. The larger the stage number was,the higher the sensitivity was. The development was conducted by dippingthe photosensitive material in the following developer at 25° C. for 10seconds.

    ______________________________________                                        DP-4 (produced by Fuji Photo Film Co.,                                                                 66.5   g                                             Ltd.)                                                                         Water                    881.4  g                                             Lipomin LA (20% aq. soln., produced by                                                                 52.1   g                                             Lion Corp.)                                                                   ______________________________________                                    

The examinations of storage stability were performed as follows. Thepresence of deposits derived from the photosensitive layer was observedwith an optical microscope by using the above-described photosensitivematerial after natural aging of 1 month. Furthermore, in the samemanner, deposits were surveyed when the photosensitive material waspreserved at 50° C. in an oven.

                                      TABLE A                                     __________________________________________________________________________    Photopolymerization initiator                                                                             Sensitivity to light                                    Component Component   through BP-49 filter                                    (ii)  X g (iii)   Y g (stage number of step wedge)                      __________________________________________________________________________    Ex. 1 (a-2) 0.12 g                                                                            (D) 0.054 g 6                                                 Ex. 2 (a-2) 0.12 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           6.5                                               Ex. 3 (a-5) 0.12 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           6.5                                               Ex. 4 (a-8) 0.14 g                                                                            (E) 0.054 g + (G)                                                                     0.054 g                                                                           7                                                 Ex. 5 (a-10)                                                                              0.14 g                                                                            (E) 0.054 g + (G)                                                                     0.054 g                                                                           7.5                                               Ex. 6 (a-20)                                                                              0.15 g                                                                            (E) 0.054 g + (G)                                                                     0.054 g                                                                           7.5                                               Ex. 7 (a-2) 0.12 g                                                                            (F) 0.12 g + (H)                                                                       0.06 g                                                                           6.5                                               Ex. 8 (a-2) 0.12 g                                                                            (J) 0.12 g + (H)                                                                       0.06 g                                                                           6.5                                               Comp. Ex. 1                                                                         (A)   0.12 g                                                                            (D) 0.054 g 4.5                                               Comp. Ex. 2                                                                         (A)   0.12 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           5                                                 Comp. Ex. 3                                                                         (A)   0.12 g                                                                            (F) 0.12 g + (H)                                                                       0.06 g                                                                           4.5                                               Comp. Ex. 4                                                                         (A)   0.12 g                                                                            (J) 0.12 g + (H)                                                                       0.06 g                                                                           5                                                 Comp. Ex. 5                                                                         (B)   0.12 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           4                                                 Comp. Ex. 6                                                                         (C)   0.15 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           5.5                                               __________________________________________________________________________     ##STR71##                                                                     ##STR72##                                                                     ##STR73##                                                                     ##STR74##                                                                     ##STR75##                                                                     ##STR76##                                                                     ##STR77##                                                                      (H) 2-Mercaptobenzothiazole                                              

(J) Dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl

It is clearly seen that component (ii) of the present invention issuperior in the sensitivity to visible light as compared with thecompound for comparison.

EXAMPLES 9 TO 20 AND COMPARATIVE EXAMPLES 1 TO 7

On the surface of an aluminum plate treated in the same manner as inExamples 1 to 8, the photosensitive composition having the followingcomposition was coated to give a dry coated weight of 1.4 g/m² and driedat 80° C. for 2 minutes to form a photosensitive layer.

    ______________________________________                                        Trimethylolpropane triacrylate                                                                         2.0    g                                             Allyl methacrylate/methacrylic acid                                                                    2.0    g                                             copolymer (copolymer molar ratio: 80/20)                                      Component (ii)           X      g                                             Component (iii)          Y      g                                             Fluorine-base nonionic surface active                                                                  0.03   g                                             agent (F-177, produced by Da-Nippon Ink &                                     Chemicals, Inc.)                                                              Thermal polymerization inhibitor:                                                                      0.01   g                                             N-nitrosophenylhydroxylamine                                                  aluminum salt                                                                 Pigment dispersion       2.0    g                                             Composition                                                                   Copper phthalocyanine    30     parts                                         Allyl methacrylate/      20     parts                                         methacrylic acid copolymer                                                    (copolymer molar ratio:                                                       83/17)                                                                        Cyclohexanone            35     parts                                         Methoxypropyl acetate    35     parts                                         Propylene glycol monomethyl                                                                            80     parts                                         ether                                                                         Methyl ethyl ketone      20     g                                             Propylene glycol monomethyl ether                                                                      20     g                                             ______________________________________                                    

The specifications of component (ii) and component (iii) are describedin Table B below.

On the thus-formed photosensitive layer, a 3 wt % aqueous solution ofpolyvinyl alcohol (saponification degree: 98 mol %, polymerizationdegree: 1,000) was coated to give a dry coated weight of 2 g/m² and thendried at 100° C. for 2 minutes to provide a protective layer.

FUJI PS Step Guide (a gray scale having ΔD=0.15 and discontinuouslychanged in the transmission density, manufactured by Fuji Photo FilmCo., Ltd.) was put into close contact with the photosensitive materialobtained above and light for exposure was irradiated thereon.

The light source used was a xenon lamp and light was irradiated throughKenko Optical Filter BP-53. The energy on the PS Step Guide surface was0.25 mJ/cm².

The exposed photosensitive material was heated at 120° C. for 20 secondsand then developed. The sensitivity was shown by a clear stage numberafter development of the PS Step Guide. The larger the stage number was,the higher the sensitivity was. The development was conducted by dippingthe photosensitive material in the following developer at 25° C. for 10seconds.

    ______________________________________                                        DP-4 (produced by Fuji Photo Film Co.,                                                                 66.5   g                                             Ltd.)                                                                         Water                    881.4  g                                             Lipomin LA (20% aq. soln., produced by                                                                 52.1   g                                             Lion Corp.)                                                                   ______________________________________                                    

The examinations of storage stability were performed as follows. Thepresence of deposits derived from the photosensitive layer was observedwith an optical microscope by using the photosensitive material afternatural aging of 1 month. Furthermore, in the same manner, deposits weresurveyed when the photosensitive material was preserved at 50° C. in anoven.

                                      TABLE B                                     __________________________________________________________________________    Photopolymerization initiator                                                                             Sensitivity to light                                    Component Component   through BP-49 filter                                    (ii)  X g (iii)   Y g (stage number of step wedge)                      __________________________________________________________________________    Ex. 9 (a-25)                                                                              0.15 g                                                                            (D) 0.054 g 7                                                 Ex. 10                                                                              (a-25)                                                                              0.15 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           7.5                                               Ex. 11                                                                              (a-25)                                                                              0.15 g                                                                            (F) 0.16 g + (H)                                                                       0.06 g                                                                           7                                                 Ex. 12                                                                              (a-25)                                                                              0.15 g                                                                            (J) 0.17 g + (H)                                                                       0.06 g                                                                           7.5                                               Ex. 13                                                                              (a-26)                                                                              0.16 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           8                                                 Ex. 14                                                                              (a-28)                                                                              0.16 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           8                                                 Ex. 15                                                                              (a-31)                                                                              0.17 g                                                                            (E) 0.054 g + (G)                                                                     0.054 g                                                                           8.5                                               Ex. 16                                                                              (a-33)                                                                              0.17 g                                                                            (E) 0.054 g + (G)                                                                     0.054 g                                                                           8                                                 Ex. 17                                                                              (a-34)                                                                              0.18 g                                                                            (E) 0.054 g + (G)                                                                     0.054 g                                                                           8.5                                               Ex. 18                                                                              (a-39)                                                                              0.19 g                                                                            (E) 0.054 g + (G)                                                                     0.054 g                                                                           8                                                 Ex. 19                                                                              (a-40)                                                                              0.16 g                                                                            (E) 0.054 g + (G)                                                                     0.054 g                                                                           8                                                 Ex. 20                                                                              (a-42)                                                                              0.17 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           8.5                                               Comp. Ex. 1                                                                         (K)   0.15 g                                                                            (D) 0.054 g 5                                                 Comp. Ex. 2                                                                         (K)   0.15 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           5.5                                               Comp. Ex. 3                                                                         (K)   0.15 g                                                                            (F) 0.12 g + (H)                                                                       0.06 g                                                                           5                                                 Comp. Ex. 4                                                                         (K)   0.15 g                                                                            (J) 0.12 g + (H)                                                                       0.06 g                                                                           5.5                                               Comp. Ex. 5                                                                         (L)   0.16 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           5.5                                               Comp. Ex. 6                                                                         (M)   0.17 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           5.5                                               Comp. Ex. 7                                                                         (N)   0.17 g                                                                            (D) 0.054 g + (G)                                                                     0.054 g                                                                           5.5                                               __________________________________________________________________________     ##STR78##                                                                     ##STR79##                                                                     ##STR80##                                                                     ##STR81##                                                                      (D), (E), (F), (G), (H), and (J) were the same as those used in         

It is clearly seen that component (ii) of the present invention issuperior in the sensitivity to visible light as compared with thecompound for comparison.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A photopolymerizable composition comprising thefollowing components (i), (ii) and (iii):(i) a compound having at leastone addition-polymerizable ethylenically unsaturated bond; (ii) acompound represented by the following formula (I): ##STR82## wherein Rrepresents a halogen atom, an alkyl group, a substituted alkyl group, anaryl group, a substituted aryl group or a substituted carbonyl group;R¹and R² each independently represents an alkyl group, a substituted alkylgroup, an aryl group or a substituted aryl group; R³, R⁴, R⁵ and R⁶ eachindependently represents a hydrogen atom, a hydroxyl group, an alkylgroup, a substituted alkyl group, a substituted oxy group or asubstituted thio group; or R¹ and R³, or R² and R⁵ may be combined witheach other to form a ring structure; R⁷, R⁸, R⁹ and R¹⁰ eachindependently represents a hydrogen atom, a halogen atom, an alkylgroup, a substituted alkyl group, an aryl group, a substituted arylgroup, a hydroxyl group, a substituted oxy group, a mercapto group, asubstituted thio group, an amino group, a substituted amino group, asubstituted carbonyl group, a substituted sulfonyl group, a cyano groupor a nitro group; or R⁷ and R⁸, R⁸ and R⁹, or R⁹ and R¹⁰ may be combinedwith each other to form an aliphatic or aromatic ring; and m represents0 or 1; and (iii) an activating agent which generates an active radicalupon light irradiation in the co-presence of component (ii).
 2. Aphotopolymerizable composition as claimed in claim 1, wherein theactivating agent is a compound having a carbon-halogen bond.